WO2020171509A1 - Electrode for electrolysis - Google Patents

Abstract

The present invention provides an electrode for electrolysis, using a planarized metal substrate so as to increase the surface area of a coating layer, thereby increasing adhesion with a membrane, and reduce a gas trap, thereby preventing overvoltage.

Description

Electrode for Electrolysis

Mutual citation with related applications

This application claims the benefit of priority based on Korean Patent Application No. 10-2019-0021361 filed on February 22, 2019, and all contents disclosed in the documents of the Korean patent application are incorporated as part of this specification.

Technical field

The present invention relates to an electrode for electrolysis and a method for manufacturing the same, and to an electrode for electrolysis in which a metal base layer of the electrode is planarized, and a method for manufacturing the same.

A technology for producing hydroxide, hydrogen and chlorine by electrolyzing inexpensive brine such as seawater is widely known. This electrolysis process is commonly referred to as a chlor-alkali process, and it can be said that the performance and reliability of technology have been proven through commercial operation for decades.

In the electrolysis of such brine, an ion exchange membrane is installed inside the electrolyzer to divide the electrolyzer into a cation chamber and an anion chamber, and the ion exchange membrane method that obtains chlorine gas from the anode and hydrogen and caustic soda from the cathode using brine as an electrolyte is currently the most widely used. This is the method being used.

Meanwhile, the electrolysis process of brine is performed through a reaction as shown in the following electrochemical reaction formula.

Positive electrode (anode) _{^{reaction: 2Cl - → Cl 2 + 2e}} - (E 0 = +1.36 V)

A negative electrode (cathode) ^{_{reaction: 2H 2 O + 2e - →}} 2OH - + H 2 (E 0 = -0.83 V)

Total _{^{reaction: 2Cl - + 2H 2 O →}} 2OH - + Cl 2 + H 2 (E 0 = -2.19 V)

In performing the electrolysis of brine, the electrolytic voltage should consider both the voltage required for the theoretical brine electrolysis, the overvoltage of the anode, the overvoltage of the cathode, the voltage by the resistance of the ion exchange membrane, and the voltage by the distance between the anode and the cathode. Among these voltages, the overvoltage caused by the electrode acts as an important variable.

Therefore, a method to reduce the overvoltage of the electrode is being studied. For example, a precious metal electrode called DSA (Dimensionally Stable Anode) has been developed and used for the anode, and the development of excellent materials with low overvoltage and durability for the cathode. Is being demanded.

Stainless steel or nickel has been mainly used as such a cathode, and recently, to reduce overvoltage, the surface of stainless steel or nickel is coated with nickel oxide, an alloy of nickel and tin, a combination of activated carbon and oxide, ruthenium oxide, platinum, etc. The method of use is being studied.

In addition, a method of controlling the composition using a platinum group element such as ruthenium and a lanthanide element such as cerium is also being studied in order to increase the activity of the negative electrode by controlling the composition of the active material. However, an overvoltage phenomenon occurred, and a problem occurred in which deterioration due to reverse current occurred.

Prior art literature

(Patent Document 1) JP2003-2977967A

An object of the present invention is to provide an electrode for electrolysis in which overvoltage is improved by increasing adhesion to a membrane and reducing gas traps.

In order to solve the above problems, the present invention is a metal substrate layer having a mesh structure; And a coating layer comprising a ruthenium oxide, a cerium oxide, a platinum oxide, and an amine compound, wherein the coating layer is formed on a surface of the wire constituting the mesh structure, and the aspect ratio of the individual cross-sections of the wire is 120% It provides an electrode for electrolysis that is above.

In addition, the present invention comprises the steps of flattening the metal substrate having the mesh structure so that the aspect ratio of the individual cross-section of the wire constituting the mesh structure is 120% or more; Applying a coating composition on the surface of the wire of the planarized metal substrate; And drying and firing the metal substrate to which the coating composition is applied, and coating the coating composition, wherein the coating composition comprises a ruthenium-based precursor, a cerium-based precursor, a platinum-based precursor, and an amine-based compound. Provides a way.

In the electrode for electrolysis according to the present invention, since the metal substrate is flattened, adhesion to the membrane is high, and thus, gas traps are reduced, thereby effectively enabling gas desorption, thereby improving overvoltage.

1 is a diagram schematically showing an effect that may appear when a metal substrate is flattened in the present invention.

2 is a graph showing changes in performance of electrodes of Examples 1 to 2 and Comparative Examples 1 to 2 of the present invention over time.

3 is a diagram illustrating the electrode surfaces of Example 1 and Comparative Example 2 of the present invention.

Hereinafter, examples and experimental examples will be described in more detail to describe the present invention in detail, but the present invention is not limited by these examples and experimental examples. The embodiments according to the present invention may be modified in various forms, and the scope of the present invention should not be construed as being limited to the embodiments described below. Embodiments of the present invention are provided to more completely describe the present invention to those of ordinary skill in the art.

material

In this example, a nickel substrate (Ni purity 99% or more, diameter 200 μm, thickness 370 μm) manufactured by Ildong Gold Mesh was used as the metal substrate, and the ruthenium-based precursor was Heraeus' ruthenium chloride hydrate and the platinum-based precursor. Alfa Aesar's platinum chloride (platinum (IV) chloride, 99.9%), Sigma-Aldrich's cerium nitrate hexahydrate as a cerium-based precursor, and Daejunghwa Geum's urea as an amine-based compound were used. In addition, as a solvent, isopropyl alcohol and 2-butoxy ethanol from Daejunghwa Geum were used.

Preparation of coating composition

Metal precursors RuCl ₃ ·nH ₂ O, Ce(NO ₃ ) ₃ ·6H ₂ O and PtCl ₄ are mixed in a molar ratio of 5:1:0.4, and isopropyl alcohol and 2-butoxy ethanol are mixed in a volume ratio of 1:1 It was dissolved in the mixed solvent. Thereafter, when the metal precursor was dissolved, urea, an amine compound, was added at a molar ratio of 3.13, and stirred at 50° C. overnight to prepare a coating composition solution having a concentration of 100 g/L based on ruthenium.

Example

Example 1. Preparation of Electrode for Electrolysis Using Nickel Substrate Flattened by Rolling

The nickel substrate of the material was rolled to prepare a flattened nickel substrate having a thickness of 170 μm. The aspect ratio of the cross section of the individual wire of the flattened nickel substrate was measured, and the value was 120 to 169%. Thereafter, the surface of the substrate was sandblasted with aluminum oxide (120 mesh) at 0.4 MPa to form an uneven structure. Then, the processed nickel substrate was put in a 5M H ₂ SO ₄ aqueous solution at 80° C. and treated for 3 minutes to complete the pretreatment process. Thereafter, the coating composition solution prepared above was coated on the pretreated nickel substrate by a brush method, placed in a convection drying oven at 180° C. and dried for 10 minutes, and then put in an electric heating furnace at 500° C. and fired for 10 minutes. The coating, drying, and firing processes were additionally performed 9 times, and finally, firing in an electric heating furnace heated to 500° C. for 1 hour to prepare an electrode for electrolysis.

Example 2. Preparation of Electrode for Electrolysis Using Nickel Base Flattened by Chemical Etching

Except for the fact that the chemical etching was performed instead of rolling in Example 1, the electrode for electrolysis was prepared in the same manner. The aspect ratio of the cross section of the individual wire of the flattened nickel substrate was measured, and the value was 132 to 155%.

Example 3. Preparation of Electrode for Electrolysis Using Nickel Substrate Flattened by Press

In Example 1, except that instead of rolling, pressing was performed in the same manner to prepare an electrode for electrolysis. However, in the case of press treatment, flattening was not performed consistently compared to the case of flattening by other methods, but the value of the aspect ratio was 120 to 180%, which was found to be larger than that of flattening by other methods.

Comparative Example 1. Commercial electrode

After voltage stabilization of the fresh electrode was completed through an electrolysis process, it was activated and used as a commercial electrode of Comparative Example 1.

Comparative Example 2. Preparation of Electrode for Electrolysis Using Non-planarized Nickel Base

Except for the fact that the planarization was not performed in Example 1, all were carried out in the same manner to prepare an electrode for electrolysis. The aspect ratio of the cross-section of the individual wires of the nickel substrate that was not flattened was 100%.

Comparative Example 3. Preparation of an electrode for electrolysis using a thin nickel base without planarization

In Example 1, except that the thickness was 170 μm and a nickel substrate that was not planarized was used, all were carried out in the same manner to prepare an electrode for electrolysis. The aspect ratio of the cross-section of the individual wires of the nickel substrate that was not flattened was 100%.

Information on the electrodes prepared in Examples 1 to 3 and Comparative Examples 1 to 3 is summarized in Table 1 below.

division	Example 1	Example 2	Example 3	Comparative Example 1	Comparative Example 2	Comparative Example 3
Planarization method	Rolling	Chemical etching	Press	-	-	-
Aspect ratio	120-169%	132-155%	120-180%	100%	100%	100%
Substrate thickness (㎛)	170	180	160	330	380	170
Composition ratio of coating layer (Ru:Ce:Pt:urea)	5:1:0.4:3.13	5:1:0.4:3.13	5:1:0.4:3.13	5:1:0.4:3.13	5:1:0.4:3.13	5:1:0.4:3.13

Experimental Example 1. Performance check of the prepared electrode for electrolysis

In order to check the performance of the electrodes prepared in Examples 1 to 3 and Comparative Examples 1 to 3, a single cell device for measuring overvoltage at a constant current was used. AKC's oxidation electrode, which is the electrode used, was used as the anode, and the cathode was measured using a 5X5cm ² cell capable of realizing a zero gap cell in the form of a nickel mattress mounted on a current meter and an electrode raised. I did. Aciplex's F6808 was used as the membrane, and the experiment was performed at a current density of 6.2kA/m ² as a constant current. A cathode voltage measurement experiment was performed using a half-cell in Chlor-Alkali Electrolysis. 305 g/L of sodium chloride was used as the electrolyte on the oxidizing electrode side, and 30.6% sodium hydroxide was used as the electrolyte on the reduction electrode side. The reaction temperature was set to 90° C., and the experiment was performed while flowing a flow rate of 15 ml/min for both the oxidation electrode and the reduction electrode. The results are summarized in Table 2 below, and the changes over time are shown in FIG. 2.

	Example 1	Example 2	Example 3	Comparative Example 1	Comparative Example 2	Comparative Example 3
Performance (V)	3.040	3.035	3.043	3.086	3.045	3.126

As can be seen in Table 2, it was confirmed that the electrode of the Example having an aspect ratio of 120% or more exhibited a lower overvoltage than the electrode of the Comparative Example which was not subjected to the planarization treatment. In addition, as shown in FIG. 2, the electrode of Comparative Example 1 exhibited a high overvoltage from the beginning, and the electrodes of Examples 1 and 2 exhibited lower values than the electrode of Comparative Example 2 at the convergent overvoltage value after a certain period of time. Confirmed the point.

Experimental Example 2. Surface observation of electrode

The surfaces of the electrodes prepared in Example 1 and Comparative Example 2 were observed, and this is shown in FIG. 3. Observation was performed through a SEM (Scanning Electron Microscope). From FIG. 3, it was confirmed that the wires intersecting in the mesh structure contacted in a large area, and thus a coating layer having a larger area can be secured. That is, it was confirmed that the electrode of Example 1 could smoothly perform the electrolysis reaction compared to Comparative Example 2.

Hereinafter, the present invention will be described in more detail.

The terms or words used in the present specification and claims should not be construed as being limited to their usual or dictionary meanings, and the inventor may appropriately define the concept of terms in order to describe his own invention in the best way. It should be interpreted as a meaning and concept consistent with the technical idea of the present invention based on the principle that there is.

Definition of Terms

As used herein, “aspect ratio” refers to the ratio of width to height (width/height).

As used herein, "mesh structure" refers to a mesh structure formed by intertwining wires.

Electrode for Electrolysis

The present invention is a metal substrate layer having a mesh structure; And a coating layer comprising a ruthenium oxide, a cerium oxide, a platinum oxide, and an amine compound, wherein the coating layer is formed on a surface of the wire constituting the mesh structure, and the aspect ratio of the individual cross-sections of the wire is 120% It provides an electrode for electrolysis that is above.

The metal substrate may be nickel, titanium, tantalum, aluminum, hafnium, zirconium, molybdenum, tungsten, stainless steel, or alloys thereof, of which nickel is preferable. When nickel is used as a metal substrate, durability and electrode performance may be excellent.

In the metal substrate included in the electrode for electrolysis, the individual wires constituting the mesh structure thereof are planarized so that the aspect ratio of each wire cross section is 120% or more. Preferably, the lower limit of the aspect ratio may be 120%, 125%, or 130%, and the upper limit of the aspect ratio may be 180%, 170%, 160% or 150%. As can be seen from FIG. 1, when the aspect ratio of the cross-section of individual wires constituting the mesh structure is set to be 120% or more by flattening the metal substrate having the mesh structure, the adhesion to the membrane increases, thereby reducing gas traps, and consequently reducing overvoltage. It can be improved, and a smooth electrolysis reaction can be carried out. On the other hand, if the aspect ratio is too large, there may be a problem that the durability of the metal substrate itself is weakened. Planarization can be performed without limitation of the method, as long as the aspect ratio of the cross-section of individual wires constituting the mesh structure can be increased to 120% or more without affecting the durability of the metal substrate, and preferably through pressing, rolling or chemical etching. Can be done.

The ruthenium-based oxide, cerium-based oxide, and platinum-based oxide of the coating layer play a role of lowering the overvoltage of the electrode, and in particular, the platinum-based oxide can further improve the stability of the catalyst layer to improve overvoltage, and the cerium-based oxide is durable and the catalyst layer It can improve stability.

The thickness of the metal substrate may be 100 to 300㎛, preferably 120 to 280㎛, more preferably 150 to 250㎛. If the metal substrate is too thin, for example, if it is thinner than 100 μm, the durability of the electrode may be weak and there may be a problem in use. If the metal substrate is too thick, for example, if it exceeds 300 μm, a lot of cost is consumed in manufacturing the electrode. If a metal substrate having a thick mesh structure is used, the hardness of the substrate is high, so that the adhesion between the electrode and the membrane in the zero-gap cell decreases, and thus the electrolysis reaction may not occur smoothly.

Method of manufacturing electrode for electrolysis

The present invention comprises the steps of flattening the metal substrate having the mesh structure so that the aspect ratio of individual cross-sections of the wires constituting the mesh structure is 120% or more; Applying a coating composition on the surface of the wire of the planarized metal substrate; And drying and firing the metal substrate to which the coating composition is applied, and coating the coating composition, wherein the coating composition comprises a ruthenium-based precursor, a cerium-based precursor, a platinum-based precursor, and an amine-based compound. Provides a way.

The planarization may be performed through the same method as described above, and is preferably performed through rolling or chemical etching.

The ruthenium-based precursor is a material that provides ruthenium as an active material in the catalyst layer of the cathode for electrolysis. The ruthenium-based precursor is ruthenium hexafluoride (RuF ₆ ), ruthenium (III) chloride (RuCl ₃ ), ruthenium (III) chloride hydrate (RuCl ₃ xH ₂ O), ruthenium (III) bromide (RuBr ₃ ), ruthenium (III) bromide hydrate (RuBr ₃ xH ₂ O), ruthenium iodide (RuI ₃ ) and may be one or more selected from the group consisting of a ruthenium acetate salt, of which ruthenium (III) chloride hydrate is preferred.

The cerium-based precursor is a material that provides a cerium element to the catalyst layer of the cathode for electrolysis. The cerium element can improve the durability of the electrolysis negative electrode to minimize the loss of ruthenium in the catalyst layer of the electrolysis electrode during activation or electrolysis. Specifically, when the cathode for electrolysis is activated or electrolyzed, particles containing ruthenium in the catalyst layer become metallic Ru (metallic Ru) without changing the structure or partially hydrated to reduce to active species. do. In addition, the structure of the particles containing the cerium element in the catalyst layer is changed to form a network with the particles containing ruthenium in the catalyst layer, and as a result, the durability of the cathode for electrolysis can be improved, thereby preventing the loss of ruthenium in the catalyst layer. .

The cerium-based precursors are cerium (III) nitrate hexahydrate (Ce (NO ₃ ) ₃ · 6H ₂ O), cerium (IV) sulfate tetrahydrate (Ce (SO ₄ ) ₂ · 4H ₂ O) and cerium (III) It is at least one selected from the group consisting of chloride heptahydrate (CeCl ₃ 7H ₂ O), and cerium (III) nitrate hexahydrate is preferable.

The catalyst composition may include 0.01 to 0.5 moles or 0.05 to 0.35 moles of the cerium-based precursor per 1 mole of the ruthenium-based precursor, of which 0.05 to 0.35 moles is preferably included.

If the above-described range is satisfied, the durability of the electrode to be manufactured can be improved to minimize the loss of ruthenium in the catalyst layer during activation or electrolysis.

The platinum-based precursor is a material that provides platinum to the catalyst layer of the cathode for electrolysis. The platinum may improve the overvoltage phenomenon of the electrode. In addition, the platinum can minimize the deviation of the initial performance of the electrode and the performance after a certain period of time, and as a result, the electrode does not perform a separate activation process or can be minimized.

The platinum-based precursors are chloroplatinic acid hexahydrate (H ₂ PtCl ₆ 6H ₂ O), diamine dinitro platinum (Pt(NH ₃ ) ₂ (NO) ₂ ) and platinum (IV) chloride (PtCl ₄ ), platinum ( II) chloride (PtCl ₂ ), potassium tetrachloroplatinate (K ₂ PtCl ₄ ), potassium hexachloroplatinate (K ₂ PtCl ₆ ) It may be one or more selected from the group consisting of, of which platinum (IV) chloride Is preferred.

The catalyst composition may contain the platinum-based precursor in an amount of 0.01 to 0.7 moles or 0.02 to 0.5 moles per 1 mole of the ruthenium-based precursor, of which 0.02 to 0.5 moles is preferably included.

If the above-described range is satisfied, the overvoltage phenomenon of the electrode can be remarkably improved. In addition, since the initial performance of the electrode and the performance after a certain period of time can be kept constant, the electrode activation process is unnecessary. Accordingly, it is possible to reduce the time and cost required for the electrode activation process.

The amine-based compound is known to play a role of reducing the particle phase by introducing it as an additive when preparing nanoparticles, etc., and exhibits an effect of making the ruthenium oxide crystal phase smaller even in electrode coating. In addition, since the catalyst composition contains an amine-based compound, the cerium network structure formed by increasing the size of the acicular structure of cerium plays a role in fixing the ruthenium particles more firmly, thereby improving the durability of the electrode. And, as a result, even when the electrode is operated for a long time, there is an effect of remarkably reducing the peeling phenomenon of the electrode.

The catalyst composition may contain 0.5 to 1 mole or 0.6 to 0.9 mole of the amine compound per 1 mole of the ruthenium-based precursor, of which 0.6 to 0.9 mole is preferably included.

When the above-described content is satisfied, the amine-based compound changes the structure of the particles containing cerium element faster than when the amine-based compound is not used after activation of the electrode or during electrolysis to form a network in the catalyst layer. And, as a result, the durability of the electrode can be improved. Specifically, the amine-based compound may improve the durability of the electrode by increasing the acicular structure of particles containing cerium.

It is preferable that the amine compound is urea. When urea is used, compared to other amine-based compounds, the stability and safety of the coating solution are excellent, and there are advantages of less generation of harmful substances and odors even when manufacturing an electrode in a large area.

In the manufacturing method of the present invention, it may include a step of pretreating the metal substrate before performing the coating step.

The pretreatment may be to form irregularities on the surface of the metal substrate by chemical etching, blasting, or thermal spraying of the metal substrate.

The pretreatment may be performed by sand blasting the surface of the metal substrate to form fine irregularities, and salt treatment or acid treatment. For example, the surface of the metal substrate may be sandblasted with alumina to form irregularities, immersed in an aqueous sulfuric acid solution, washed and dried to pretreat to form fine irregularities on the surface of the metal substrate.

The application is not particularly limited as long as the catalyst composition can be evenly applied on the metal substrate, and may be performed by a method known in the art.

The application may be performed by any one method selected from the group consisting of doctor blade, die casting, comma coating, screen printing, spray spraying, electrospinning, roll coating, and brushing.

The drying may be performed at 50 to 300°C for 5 to 60 minutes, preferably at 50 to 200°C for 5 to 20 minutes.

If the above-described conditions are satisfied, the solvent can be sufficiently removed while minimizing energy consumption.

The sintering may be performed at 400 to 600° C. for 1 hour or less, and is preferably performed at 450 to 550° C. for 5 to 30 minutes.

The firing serves to convert a metal precursor into an oxide. When sintering satisfies the above-described conditions, impurities in the catalyst layer are easily removed, and strength of the metal substrate may not be affected.

Meanwhile, the coating may be performed by sequentially repeating application, drying, and firing so that the amount of ruthenium per unit area (m 2) of the metal substrate is 10 g or more. That is, in the manufacturing method according to another embodiment of the present invention, after applying, drying and firing the catalyst composition on at least one surface of a metal substrate, it is applied again on one surface of the metal substrate to which the first catalyst composition is applied, and dried. And coating to be fired can be repeatedly performed. The repetition may be performed 5 to 20 times.

Claims (10)

1. A metal substrate layer having a mesh structure; And

   Including a coating layer containing a ruthenium-based oxide, a cerium-based oxide, a platinum-based oxide and an amine-based compound,

   The coating layer is formed on the surface of the wire constituting the mesh structure,

   The aspect ratio of the individual cross-section of the wire is 120% or more of the electrode for electrolysis.
2. The electrode for electrolysis according to claim 1, wherein the aspect ratio is 120 to 180%.
3. The electrode according to claim 1, wherein the metal is nickel, titanium, tantalum, aluminum, hafnium, zirconium, molybdenum, tungsten, stainless steel, or an alloy thereof.
4. The electrode according to claim 1, wherein the thickness of the metal substrate layer is 100 to 300 μm.
5. Flattening the metal substrate having the mesh structure so that the aspect ratio of the individual cross-sections of the wires constituting the mesh structure is 120% or more;

   Applying a coating composition on the surface of the wire of the planarized metal substrate; And

   It includes the step of drying and firing the metal substrate coated with the coating composition to coat,

   The coating composition is a method of manufacturing an electrode for electrolysis comprising a ruthenium-based precursor, a cerium-based precursor, a platinum-based precursor, and an amine-based compound.
6. The method of claim 5, wherein the planarization is performed through rolling or chemical etching.
7. The method of claim 5, wherein the metal substrate is nickel.
8. The method of claim 5,

   The ruthenium-based precursor is ruthenium hexafluoride (RuF ₆ ), ruthenium (III) chloride (RuCl ₃ ), ruthenium (III) chloride hydrate (RuCl ₃ xH ₂ O), ruthenium (III) bromide (RuBr ₃ ), ruthenium (III) bromide hydrate (RuBr ₃ ·xH ₂ O), ruthenium iodide (RuI ₃ ) and at least one selected from the group consisting of ruthenium acetate salt,

   The cerium-based precursors are cerium (III) nitrate hexahydrate (Ce (NO ₃ ) ₃ · 6H ₂ O), cerium (IV) sulfate tetrahydrate (Ce (SO ₄ ) ₂ · 4H ₂ O) and cerium (III) At least one selected from the group consisting of chloride heptahydrate (CeCl ₃ 7H ₂ O),

   The platinum-based precursors are chloroplatinic acid hexahydrate (H ₂ PtCl ₆ 6H ₂ O), diamine dinitro platinum (Pt(NH ₃ ) ₂ (NO) ₂ ) and platinum (IV) chloride (PtCl ₄ ), platinum ( II) Chloride (PtCl ₂ ), potassium tetrachloroplatinate (K ₂ PtCl ₄ ), potassium hexachloroplatinate (K ₂ PtCl ₆ ) One or more selected from the group consisting of a method for producing an electrode for electrolysis.
9. The method of claim 5, wherein the amine-based compound is urea.
10. The method of claim 5, wherein the coating, drying, and firing are each repeatedly performed 5 to 20 times.

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